Stable ceramic consisting of aluminum oxide

ABSTRACT

A ceramic consisting substantially of Al 2  O 3  as ceramic support, ceramic cover layer and/or ceramic supporting structure for heating conductors is described, which is electrochemically stable, which, in other words, does not decompose on application of a heating voltage, even in long-term operation at temperatures above 600°. Such a ceramic exhibits a very small alkali metal content, of less than 0.2% by weight Na 2  O and K 2  O respectively. Particularly favorable processing, in particular pressing properties are exhibited by such a ceramic if it has 2.5 to 10% by weight of barium silicate or strontium silicate fluxes, the proportions of Na 2  O, K 2  O, CaO and MgO together make up less than 1% by weight, and the BaO or SrO:SiO 2  molar ratio is between 2:1 and 1:12.5. Such a ceramic with a BaO:SiO 2  ratio of 2.6:1 parts by weight is electrochemically stable up to approximately 1400° C., and at 1300° C. still exhibits a bending strength of approximately 300 N/mm 2 .

BACKGROUND OF THE INVENTION

The invention relates to an alumina ceramic and, more particularly, to a ceramic made of alumina with a low alkali metal oxide content for heating conductors. Ceramic components with integrated heating conductors in the form of printed patterns consisting of a cermet are endangered by electrochemical decomposition of the carrier ceramic, of the ceramic cover layer and/or of the ceramic supporting structure. The electrolytic decomposition is produced by ionic conduction under the applied heating voltage, which is, for example, below 24 V direct-current voltage in the case of motor-vehicle applications, and can finally lead to the destruction of the heating conductor on account of the separation of cations with alloy formation and/or by separation of oxygen with oxide formation or by crack formation on account of the excess oxygen pressure arising below the insulating cover layer. This applies all the more the higher is the application temperature, and can become critical at temperatures as low as 600° C. Such ceramic components with integrated heating conductors are used, for example, in sheathed-element glow plugs, in lambda probes or similar electrochemical sensors, in heated nozzles for various intended applications and in continuous-flow heaters for boilers or coffee machines in the form of small plate-shaped, pin-shaped or tubular heaters.

Aluminium oxide, as it is available in the trade, normally contains up to 0.5% by weight sodium oxide and/or potassium oxide. Usually, the aluminium oxide is used in this form, especially in mass-produced products, because the purer specifications of the aluminium oxide are far more expensive, as compared with those mentioned.

SUMMARY OF THE INVENTION

According to our invention an electrochemically stable ceramic used for making a ceramic support, a ceramic coating layer and a ceramic support skeleton for a heating conductor comprises alumina with alkali metal oxides and from 2.5 to 10 percent by weight of a flux consisting essentially of a barium silicate with a BaO:SiO₂ molar ratio of from 2:1 and and 1:12.5, the sum of the Na₂ O, K₂ O, CaO and MgO content being less than 1 percent by weight, while the sum of the Na₂ O and K₂ O, CaO and MgO are initially present as impurities in the barium silicate and the alumina. Our invention has the advantage that it is electrochemically stable in long-term operation at the applied direct-current voltage at temperatures up to 1400° C., that is to say that it shows no ceramic decomposition and/or heating-conductor damage due to cation migration or oxygen separation. Thus, of course, the appropriate components in which such a ceramic is used exhibit a substantially longer service life.

Advantageous further developments and improvements of the aluminium oxide ceramic indicated in the main claim are possible by means of the measures recited in the subclaims. It is particularly advantageous if the Al₂ O₃ ceramic contains less than 0.1% by weight Na₂ O and K₂ O respectively. Although both a ceramic without flux and also a ceramic with small quantities of flux may be produced from the aluminium oxide mentioned, a ceramic with a content of fluxes of 2.5-10% by weight is indeed particularly preferred, the proportions of Na₂ O, K₂ O, CaO amd MgO being below 1% by weight and ions which are relatively large and which therefore move only with difficulty, i.e. principally barium and strontium, being included in the flux, in other words the flux being present in the form of a barium silicate and/or of a strontium silicate. In this case, the BaO or SrO/SiO₂ molar ratio can be between 2:1 and 1:12.5.

EXAMPLES

The text which follows contains a description of three embodiments, namely one for an Al₂ O₃ ceramic without flux, a second for an Al₂ O₃ ceramic with small quantities of flux and finally a third for an Al₂ O₃ ceramic with a flux consisting of barium silicate. Since the work-up of the mass took place in the same way in all cases, this work-up is described first to cover all cases. The weighedout components are ground in the dry state, together with a grinding promotor additive of 1% propandiol, in a Vibratom mill for three hours. The pressing mass is then produced therefrom, e.g., by freeze-drying an aqueous suspension of the ground material with the addition of organic binding agents, and further processed in the manner then provided, for the assessment of the electrochemical stability, for example in that a Pt/Al₂ O₃ heating-conductor layer with an Al₂ O₃ insulating cover layer was applied to a presintered component and sintered. The assessment of the electrochemical stability took place as follows: A test temperature was set by increasing the heating voltage and a determination was made as to whether the structure is still electrochemically stable at this test temperature, namely by respective measurement of resistance and breakdown strength of cover layer and/or heating conductor as well as visual determination of discolorations and cracks. This gave a limiting temperature, at which the layers investigated were no longer stable. In order to determine the strength values, appropriate test specimens were produced from the materials. The elctrochemical stability of the ceramic undergoes a further increase, if it is annealed after sintering and specifically at 1250° C. for from one to three hours.

1ST EXAMPLE Al₂ O₃ ceramic without flux

The 1st example was represented by an aluminium oxide having a content of 99.5% Al₂ O₃, which had no more than 0.1% by weight Na₂ O and K₂ O respectively. Up to approximately 800° C., this material exhibits a bending strength of 420N/mm², and at 1200° C. a bending strength of approximately 300N/mm². The testing of the electrochemical stability gave a limiting temperature of 1400° C.

This ceramic free from flux must, however, be sintered at high sintering temperatures (1600° C.), or very expensive Al₂ O₃ raw materials with increased sintering activity must be used. The processing properties of such masses free from flux are, moreover, relatively poor, as is known.

2ND EXAMPLE Al₂ O₃ ceramic with a flux

This example involves an Al₂ O₃ ceramic having a larger proportion of flux and ions contained therein which are relatively immobile, because they are large. This example represent a particularly preferred variant of the ceramic according to the invention, because, besides the electrochemical stability, it exhibits as compared with the previously mentioned examples, improved processing properties, in particular a more favourable pressing behaviour. The ceramic indicated by way of example has the following composition: 91.0% by weight Al₂ O₃ ; 6.48% by weight BaO and 2.52% by weight SiO₂ ; this corresponds to a BaO:SiO₂ ratio of 2.6:1 parts by weight or of 1:1 moles. Since alkali metal and CaO or MgO proportions are to remain below one per cent by weight and alkali metal proportions themselves below 0.2% weight, an aluminium oxide having 99.5% Al₂ O₃ is used. The barium oxide is introduced in the form of barium carbonate, and the SiO₂ component at least predominantly as kaolinite or halloysite; this leads to favourable production and pressing properties. The components mentioned are treated and tested as described above. When a direct-current voltage of 12.5 V was applied, this ceramic showed itself to be electrochemically stable up to 1400° C., in a long-term test, when used both as supporting structure for heating conductors and also for covering the semiconductor. Moreover, an increased strength is surprisingly to be found at temperatures above 1000° C.; indeed, in this case a bending strength of 300N/mm² is achieved at 1300° C. The slight decrease of the strength at these high temperatures is attributable to an extensive crystallizing-out of the glass phase. This ceramic already sinters at 1525° C. to 96% of the theoretical density (estimated from the phase analysis).

While our invention has been illustrated and described as embodied in a ceramic, it is not intended to be limited to the details of the examples described above, since various modifications and changes may be made without departing in any way from the spirit of our present invention.

Without further analysis, the foregoing will so fully reveal the gist of our present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of the prior art, farily constitute essential characteristics of the generic or specific aspects of this invention. 

What is claimed as new and desired to be protected by Letters Patent is set forth the appended claims:
 1. In an electrochemically stable ceramic comprising alumina with alkali metal and alkaline earth metal oxides used for making a ceramic support, ceramic coating layer and a ceramic support skeleton for a heating conductor, the improvement consisting of adding from 2.5 to 10 percent by weight of a flux consisting essentially of a barium silicate with a BaO:SiO₂ molar ratio of from 2:1 and 1:12.5, the sum of Na₂ O, K₂ O, CaO and MgO content being less than 1 percent by weight while the sum of said Na₂ O and K₂ O content is less than 0.2 percent by weight, said Na₂ O, K₂ O, CaO and MgO being initially present as impurities in said barium silicate and said alumina.
 2. The improvement defined in claim 1 wherein said sum of said Na₂ O and K₂ O contents is less than 0.1% by weight.
 3. The improvement defined in claim 1 wherein said SiO₂ has been introduced as kaolinite and BaO as carbonates.
 4. The improvement defined in claim 1 wherein said SiO₂ has been introduced as halloysite and BaO as carbonates. 